Germicidal detergent



agents being present in a very minor propor ion;

Patented Nov. 25, 1941 UNITED STATES PATENT GERMICIDAL DETERGENT Halvor0. Halvorson, Minneapolis, Minn., Erling J. Ordal, Seattle, Wash, andJohn L. Wilson,

Examiner devi 1 This invention relates to improved germicidaldetergents.

The new and improved germicidal detergents of the present inventioninclude a wetting agent or agents, buffer or alkaline salts, and achlorine disinfecting compound, particularly an organic chlorinedisinfecting compound, in such proportions that when, for example, asolution is made of the composition containing from /2 to 3% of to 3% ofthe new composition may be varied over a relatively wide range, forexample from a of a little abov 7.0 to as hi h as lgggbut in general itis advantageous 0 use compositions which produce solutions having a pHranging from about to about 11, as such solutions have excellentdetergent properties and do not have the objections of highly causticsolutions. Furthermore, with many of the chlorine disinfecting thecomposition, the solution will be an effective 10 compounds, andparticularly with azochloramide germicidal detergent'and the wettingagent and the chlorine disinfecting compound will each form but a smallfraction of 1% of the solution.

The term wttin as used herein is intended to desi se sulfonated or sulfaproducts such as sulfonated hydrocarbons, sulfated or sulfonated higheralcohols, and sulfonated or sulfated fatty oils and fatty acids andesters thereof, which are jree from carp qgyl groups, whether free orneutralized, or which have carboxyl groups blanked or made ineffectivein asuitable manner, as by substituting for the hydrogen of the carboxylgroup an alkyl group, or an amido group, or other suitable group andnhich donut form,obieeiieneb enreci ita es calcium and magnesium ions,found in hard f'gcustiiffi iedirenswam cans. which are neutralizedcarboxyl acids and which from objectionable precipitates with calciumand magnesium ions present in hard water.

By the term "chlorinegi sinfect i gg gg npgm is meant a chlorinecontaining compound which in water furnishes availablechlq f e and yhichifil fi l' jfifitnl QQFZPOPQQ of thislibemr lion of available chlorine.Chlorine compounds of'the nature described in the Schmelkes Patent1,958,370, and defined therein as mminlilig tives of the oxidant inaredox systerr'i,)a.nd..nar=, ficillarly li dieh l ro az namidine, haveimportant advantages for use in the present invention.

The snlfated or sulfona wetting agents, when used along witlftli bu firm'al'k'aline salts and the chlorine disinfecting compounds exert asynergistic or activating effect on the chlorine j" disinfectingcompounds, such that a solution containing the wetting agent, the bufferor alkaline salts, and the chlorine disinfecting compound hasgentproperties are due largely to the sure?? alkaline salts, thesulfated of sulfonated wettin' g" tfie'irmajor function being toactivate or s ner; L gi hec disinfect pounfi th at the amount 0 compounmay be much less than would be required in the absence of the wet-(N-N-dichloro-azo-carbonamidine) the synergistic (inactivating effect ofthe wetting agent is most marked at about this pH range.

The buffer or alkaline salts which are used in the 'new compositions ofthe invention are the alkali metal alkaline salts, such as the sodiumcarbonates, phosphates or silicates, etc., used in such amounts as toimpart the desired pH to solutions ofthe composition and to giveeffective detergent action when the compositions are dissolved in waterin a concentration of from about /2 to 3%. In using the buffer salts, inmaking the new compositions, the desired 2H and i l 1 e desird-detergent properties may, in some cases, beobtained by the employmentof a'slngle buffer salt, such as sodium c rlgonate, or mixtures pf saltsofthesame ,fsuchassodium carbonate and sodiurn bicarbonate, or salts ofdifferent acidsfsu'ch as mixtures of sodium carbonate and sodiumsilicate, or sodium carbonate and sodium phosphate. Thus thebuiler o ralkalinesalts may consist of mixtures of various phosphates andcarbonates, or phds'phat'es'T'and silicates, .or carcompositionsarethsulfonated or sulfated wet ting agents, includingthe'aromaticsulfpnates,

the alkyl aryl sulfonates, the sulfonated or sulfate a y 01 'sofi'at'tTacid esters, the sulfated ,alcohols, the ligno-sulfonates,sulfonated or sulfated derivatives of fatty acid amides, sulfonatedmineral oils, hydrogenated aryl sulfonates, etc. In general, thesematerials are characterized by having a sulfonate or sulfate group, andby freedom from carboxylic acid groups either free or neutralized, asdistinguished from blocked, as by an ester or amido group. Ql kyl naphthylgne sulfgnates and a l l yl a}fyi,l;19li5fies are marketed undervarious trade names, such as the Nekals, the Alkanols, the Areskets, theAreskapsrthe 1 gireskfines, and the Nacconols. sulfonated and ting agentto produce a germicidal product. The alkalinity of solutions containingfrom b sulfated vegetable and animal oils are marketed as Turkey-redoil, Monopole soap, Avirol KM Extra, Presbit Oil U, etc. These areordinarily sulfated products. More drastically treated vegetable oranimal oils, containing both sulfate and sulfonate groups, are marketedas Enterol and Intrasol. Sulfated fatty acids with the car- 5 boxylicacid group blocked, as with an alkyl group to form the organic acidester, are marketed as Avirol AH Extra (the sodium salt of the sulfuricacid ester of butyl ricinoleic ester). Sulfated fatty acid amides aremarketed under the trade name Humectol C., which is the sodium salt ofthe sulfuric acid ester of oleic acid amide. Sulfonated mineral oils aremarketed under various designations, including the trade name UniversalOil 3? 200, and Epifosal. Aryl sull5 fonates, such as naphthylenesulfonates are marketed under various trade names, including Parasanol.Hydrogenated aryl sulfonates are also marketed under various tradenames. For example, Alkanol S, which is sodium tetralin sulfonate.Sulfated (sulfonated) aliphatic alcohols are widely marketed under anumber of trade names. The primary alcohol derivatives are sold undersuch trade names as Gardinols, Brilliant Avirols, Dupenols, OcenolSulfate, Lorol Sulfate, 2.3. Orvus and Dreft. Sulfates of secondaryalcohols are marketed under the trade name of Tergitols. An oleic acidderivative of isethionic acid is marketed under the trade name Igepon A.The sodium salt of abietene sulfonic acid is marketed under the tradename Neopin SS.

In general, the amount of the wetting agent which will be used in thenew compositions will be but a small proportion of the whole, such thatwhemthe compositions amissolved in water in concentrations ranging fromman a, (5 wet: ting agent will cqnstitutejgut a small frac ion" of1%oftfijblutiaa 'nheehlcrineulsinrectin compoufidis used i n-sin 1ilarquantities, and in thegir'iiicldalfltugent mana es-s5, will be presentin an amount corresponding to but a small fraction of 1%, and, ingeneral, in such amounts that in the absence of the wetting agent, thesolution would not be actively germicidal.

The new compositions are advantageously com- 4 pounded and marketed asdry compositions, in

the form of dry powders, containing the various ingredients in the formof an intimate and ho- -mogeneous admixture, such that a' definiteweight of the powder may be used to give asolution of definite strengthor definite proportions of the different ingredients. Such a dry mixtureis readily prepared, handled, shipped and stored, and when used indefinite amounts in forming solutions, insures the production of propergermicidal detergent solution.

In testing the solutions of the new compositions, the following test hasbeen used:

The dry mixture, containing the ingredients of the composition, is madeinto a'solution of from to 1% strength. To 5 cc. of this solution isadded /2 cc. of a 24 hour culture of the standard test organism,Staphylococcus aureus (Insecticide Board strain). Before the culture isadded to the test solution, it is brought to the required temperature,which in these tests has been 37 C. or such other temperature as isindicated. After the culture has been in the test solution for 5minutes, a 4 mm. loopful is removed and added to a tube of molten agarat a temperature of 45 C. and the mixture poured into a Petri plate andincubated for 48 hours, at the end of which time a count is made of thecolonies appearing on the plate. The r number of organisms originallyadded to the test Alkano] B 0.95% bufier+0.0035% Azocbloramid+0.05%

AlkanolB 0.90% bufier+0.0035% Azochloramid+0.l0%

Alkanol PF 100 l 0.95% buffer+0.0035% Azochloramid+0.05%

Alkanol PF 225 0.90% butler+0.0035% Azochloramid+0.l0%

Alkanol SA 100 0.95% bufier+0.0035% Azoehloramid-l-0.05%

Alkan SA 300 0.90% bufier+0.0035% Azochloramid-l-O.l0%

Areskap 100 70 0.95% bufier+0.0035% Azochloramld+0.05%

Areskap 100 0.90% buffer+0.0035% Azoch]oramid+ .l0%

A sket 100 solution is in the neighborhood of 500 millions. If noorganisms are killed, the loopful removed will contain in excess of10,000 organisms, and therefore the number of colonies appearing on theplate will be in excess of 10,000. If some of the organisms are killed,the number of colonies appearing on the plate will be less than 10,000.In the data reported in the following examples, the numbers indicate thecolonies appearing on the test plate after 48 hours of incubation.

The invention will be illustrated by the followand variBTrs commercialsulfatedolhfilllfonated w c;tt ingagens;"the" proportion of the buffersalts bein such as to give a R LQLabQutiLim-wt solutions of thecompositions. In the solutions tested, the proportion of the buffersalts, azochloramide and wetting agents was as shown in the followingtable, which gives the results of tests carried out at a temperature of37 C. with Staphylococcus aureus, as described above.

Activation of azochloramid by various commercial wetting agentsOrganism: Staph. aareus. temperature: 37 C. B zgeaz Commercial sodiumsesquicarbonateNazO0aNaHCOa- Plate counts Solution tested 5 min. 10 min.

0.95% buffer 10, 000 10,000+ .0035% Azochloramim. 10.000 5, 000 0.95%buffer+0.0035% Azochloramid l. 500 90 re 0.95% buflerfl-0.0035%Azochloram'd+0 05% Aresket 0.90% bufler+0.0035% Azochlora d Aresklene400 0.95% buffer+0.0035% Azochloramid+0.05% oltt t l" .daaw'n"n "awi uer 5 oc orami .10 o t t t ite-give "H M u er 5 zoo orami .05

u er .0035 we loramid .10

. u er .0035 Azochloramid .05 lg iiagsgniunl f u er .0035 Azochloramld.10 0 ggrakBg dry uf ui f. u er .0035 Azochloramid .05 Ne'l'ral BX 0.90%buffer+0.0035% Azochloramid+0.l0%

Neopen SS 0.95% buifer+0.0035% Azochloramid-l-0.05%

Neopen SS 0.98% bufler+0.0035% Azochloramid+0.l0%

rvus 0.905% bufler+0.0035% Azochloramid+0.05%

rvus 0.90% bufier+0.0035% Azochloramid-i-OJO'Z,

wcocnrcwo uccccnwcsomoawpw Igepon AP 0.95% bufier+0.0035%Azochloramid+0.05%

Igepon Plate counts M Controls I 5 min. 10 min.

l/90 phenol v 7 l/l00 phenol 500 125 in examples: in,

Compositions were made up containing commercial iuml esavieerbgnatazocmoramide- Solutions of the buifer salts and wetting agents in theconcentrations outlined above, without the azochloramide, gave platecounts of 10,000 or more, except for the Nacconol KPR, which, inadmixture with the buffer salts, gave counts of 3,000 or more. From thistable it will be noted that the buffer salts alone, the buffer salt andwetting agent alone, and the buffer salts and amchloramide alone werenot effective germicidally, and that the germicidal effectiveness of theazochloramide in admixture with the buffer was radically increased bythe presence of the wetting agent. The two phenol solutions are includedfor purposes of comparison, as controls.

As further illustrating the invention, tests'were made on various buffersolutions together with an alkyl sulfate (sulfonated alcohol) andamchloramide in various concentrations. These tests were carried out inthe same manner. The results are shown in the following table:

Activation of azochloramid with an alkyl sulfate (orvus) Organisms:Staph. aureua, temperature: 37 C.

ufiers: I solution of a mix of 50% M1 00, and

50% NaHCO,, H about 9.9. II1'7 solution Na Co pH about 11.5. 1n 1 7,solution of Na=SiO H=O, pH about 12.6.

A. WITH BUFFER I, pH 9.9

Plate counts min. min.

Bufler alone 10,000+ 10,000+ Bufier+0.04% Orvus 9. 000 6, 000Bufler+0.0036% 300 Bufier+0.0036% 70 0 Bufler+{).00l8% 1,000Bufier+0.00l8% 30 Bufier+0.0009% i0, 000 Bufl'er+0.0009% 300 13. WITHBUFFER 11. pH 11.5

Plate counts 5 min. 10 min.

Buffer alone Bufier+0.04% Orvus 500 i Bufier+0.00l8% Asochloramld 3,000300 Buifer+0.0018% Azochloramid-i-0.04% Orvus. 200 3 C. WITH BUFFER III,pH 12.6

Plate counts 5 min. 10 min.

Butler alone 10, 000+ 10,000+ Butlers-0.04% Orvus 800 125 Bufier+0.0072%Azochloramid 3,000 50 Bufier+0.0072g Az'ochloramid-l-O 0rvus 100 0Bufler+0.0036 Atochloramid 8,000 200 Butl'er+0.0036% Azochloramid+0.0-i%0rvus. 100 0 Bufier+0.00l8% Azocbloramid 10, 000 1, 200 Bufier+0.00l8%Azochloram1d+0.04% Orvus 175 Plate counts Controls 5 min. 10 min.

l/90 phenol... 350 80 1/100 phenoL..- 250 70 It will be noted that thealkyl sulfate markedly increased the germicidal effectiveness of thesolution.

A further series of tests were carried out to 10 Chloram LAQHHHUE ingbuflfer salts and chloramine T or a h ritiwitl sodium lauryl sulf at eThe results are shownin the'foiiowifi'itablef Activation of chloramine Tand of a hypochlorite solution with sodium lauryl sulfate llypochlorite:HTH-15 (a commercial brand of a mixture of calcium hypochlorite andsodium carbonate which contains 15% available chlorine) made up in suchstrength that the test solutions contained 75 ppm. of availablechlorine.

15 Plate counts Solution tested 5 min 10 min.

Butler alone l0, 000+ 10,000+ 0 Sodium Ian 1 sulfate alone 10, 000+ 10,000+ Chloramine alone 0 0 Hypochlorite alone l, 000 100 Bufler+sodiumlauryl sulfate 4, 000 1, 500 Bnfler+chloramine T 10, 000 6, 500Chloramine T-l-sodiurn lsuryl sulfate 0 0 Builer+chloramine T+sodiumlauryl sulfate. 300 44 gufieri hypochlorite i. 5, 00; 2,003

0 II u 11! $1 5 ypochlonte-i-sei lum lauryl sulfate... I20 0 Platecounts Controls 5 min. 10 min.

l/OO henol 0 0 1I10fl phenol 60 3 In the foregoing test the propercomparison is between the solutions containing the chloramine T orhypochlorite and the buffer with solutions containing the chloramine Tor the hypochlorite, the buffer and the sodium lauryl sulfate, as thetests with the chloramine T or hypochlorite alone are at a much lower pHvalue than is usable in most cleaning operations. In this connection, itmust be borne in mind that the present invention relates to detergentsolutions which are germicidal, and not to simple germicidal solutions.It will be noted that the sodiumlau ryl SIL lEI mmmwsn i si sssnofn eoramine T and the hypochlori e in, sol tions containing thebuffer'saitsr' -"Tire-new compositions are useful for many purposes,such as in hospitals or similar institutions, as well as in hotels andrestaurants for dish washing and other purposes, and in variousindustries such as the beverage and dairy industries where, for example,the washing and sterilizing of bottles and containers is important.

We claim:

Amid-W811i o i on .com-

prisi ng buffer salts, a chlorine s f cting comfi'find, a d a wet in asherein defined, said composition being soluble in water, and a solutionmade therefrom, containing from to 3% of the composition, containingonly a small fraction of 1% of the wetting agent and the chlorinedisinfecting compound, being an activeluernwergent solution.

2. A germicidal detergent composition in the form of a dry mixture ofbuffer salts, a chlorine disinfecting compound and a wetting agent asherein defined, the composition being made up for the most part ofbuffer salts and containing a relatively smaller amount of the wettingagent and the chlorine disinfecting comdemonstrate the activation 01'solutions contain- 76 pound, the composition being adapted, whendissolved in water, to form a solution containing from around to 3% ofthe composition, to give an active germicidal detergent composition.

3. A germicidal detergent composition comprising bufier salts, asulfonated hydrocarbon wetting agent and a chlorine disinfectingcompound, said composition being soluble in water and being adapted,when dissolved in water to form a solution containing from around to 3%of the composition, to give an active germicidal detergent solution.

4. A germicidal detergent composition in the form of a dry mixture ofbuffer salts, a chlorine disinfecting compound and an alkyl sulfatewetting agent, the composition being made up for the most part of buiiersalts, and containing a relatively smaller amount of the chlorinedisinfecting compound and the alkyl sulfate, the composition beingadapted, when dissolved in water to form a solution containing fromaround A; to 3% of the composition, to give an active germicidaldetergent solution.

5. A germicidal detergent composition comprising bufier salts, achlorine disinfecting compound and an aromatic sulfonate, saidcomposition being soluble in water and a solution made therefrom, andcontaining from to 3%of the composition, containing only a smallfraction of 1% of the chlorine disinfecting compound and the aromaticsulfonate, being an active germicidal detergent solution.

6. A germicidal detergent composition comprising buffer salts, achlorine disinfecting compound and an alkyl aryl sulfonate, saidcomposition being soluble in water and a solution made therefrom, andcontaining from A to 3% of the composition, containing only a smallfraction of Patent No 2,265 9&8.

CERTIFICATE OF CORRECTION.

2,2ea e4s 1% of the chlorine disinfecting compound and the alkyl arylsulfonate, being an active germicidal detergent solution.

7. A germicidal detergent composition comprising bufler salts, achlorine disinfecting compound and a sulfated fatty oil, saidcomposition being soluble in. water, and a solution made therefrom, andcontaining from to 3% of the composition, containing only a smallfraction of 1% of the sulfated fatty oil and the chlorine disinfectingcompound and being an active; germicidal detergent solution.

8. Compositions as in claim 1, in which the chlorine disinfectingcompound is an N-chloro derivative of the oxidant in a redox system.

9. Compositions as in claim 1, in which the chlorine disinfectingcompound is azochloramide.

l0. Compositions as in claim 4, in which the chlorine disinfectingcompound is an N-chloro derivative of the oxidant in a redox system.

11. Compositions as in claim 6, in which the chlorine disinfectingcompound is an N-chloro derivative of the oxidant in a redox system.

12. Compositions as in claim 4, in which the chlorine disinfectingcompound is azochloramide.

l3. Compositions as in claim 6, in which the chlorine disinfectingcompound is azochloramide.

l4. Compositions as in claim 3, in which the chlorine disinfectingcompound is an N-chloro derivative of the oxidant in a redox system.

15. Compositions as in claim 3, in which the chlorine disinfectingcompound is azochloramide.

HALVOR O. HALVORSON. ERLING J. ORDAL. JOHN L. WILSON.

Novemb 5, HAL- 24 HALVOR 0. HALVORSON, ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 1,first column, line 28, .for "carboxyl" read --carboxy1ic--;

and line 29, for the word "from" read --form--; page 5, first column,line 27, for "Na SiO H O" re ad --l-Ia Si0 511 0";

and that the said. Letters Patent should be read with this correctiontherein that the same may conform to the record of the case in thePatent Office.

Signed and sealed this 5rd day of March, A. D. 19142.

(Seal) Henry Van Arsdale Acting Commissioner of Patents.

CERTIFICATE OF CORRECTION. Patent No. 2,263,948. November ?5,' 19141HALVOR O. HALVORSON, ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 1,first colximn, line 28, ,for "carboxyl" read --carbox-ylic--; and line29, for the word "from" read --form--;. page 5, first column, line 27,for "Na SiO H O" read --Na SiO 5fi O--; and that the said Letters Patentshould be read v vith this correction therein that the same may conformto the record of the case in the Patent Office.

Signed and sealed this 5rd day of March, A. D. 191m.

Henry Van Arsdale, (Seal) Acting Commissioner of Patents.

